JP6432616B2 - Method of applying heat insulating material to nozzle for continuous casting of steel - Google Patents
Method of applying heat insulating material to nozzle for continuous casting of steel Download PDFInfo
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- JP6432616B2 JP6432616B2 JP2017021934A JP2017021934A JP6432616B2 JP 6432616 B2 JP6432616 B2 JP 6432616B2 JP 2017021934 A JP2017021934 A JP 2017021934A JP 2017021934 A JP2017021934 A JP 2017021934A JP 6432616 B2 JP6432616 B2 JP 6432616B2
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- 239000011810 insulating material Substances 0.000 title claims description 62
- 238000009749 continuous casting Methods 0.000 title claims description 53
- 229910000831 Steel Inorganic materials 0.000 title claims description 41
- 239000010959 steel Substances 0.000 title claims description 41
- 238000000034 method Methods 0.000 title claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000003963 antioxidant agent Substances 0.000 claims description 44
- 230000003078 antioxidant effect Effects 0.000 claims description 44
- 239000000853 adhesive Substances 0.000 claims description 40
- 230000001070 adhesive effect Effects 0.000 claims description 35
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 27
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 22
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims 1
- 239000012774 insulation material Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910004298 SiO 2 Inorganic materials 0.000 description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000008034 disappearance Effects 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 5
- 230000001629 suppression Effects 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052863 mullite Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000004075 alteration Effects 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 2
- 230000036952 cancer formation Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 231100000504 carcinogenesis Toxicity 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- -1 Metal Si Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- GHAFORRTMVIXHS-UHFFFAOYSA-L bromosulfophthalein sodium Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(O)=CC=C1C1(C=2C=C(C(O)=CC=2)S([O-])(=O)=O)C(C(Br)=C(Br)C(Br)=C2Br)=C2C(=O)O1 GHAFORRTMVIXHS-UHFFFAOYSA-L 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 239000011214 refractory ceramic Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Products (AREA)
Description
本発明は、鋼の連続鋳造用ノズルへの断熱材の貼り付け方法に関し、更に詳細には、酸化防止材を塗布した鋼の連続鋳造用ノズルへのアルカリ土類金属系生体溶解性ファイバーから構成される断熱材の貼り付け方法に関する。 TECHNICAL FIELD The present invention relates to a method for attaching a heat insulating material to a steel continuous casting nozzle, and more specifically, an alkaline earth metal-based biosoluble fiber to a steel continuous casting nozzle coated with an antioxidant. The present invention relates to a method for attaching a heat insulating material.
鋼の連続鋳造において、取鍋中の溶鋼はロングノズルを通過し、タンディッシュへ注入される。そして、タンディッシュ中の溶鋼は浸漬ノズルの内孔を通過し、水冷モールドへと注入される。そのため、ロングノズルや浸漬ノズル本体には熱衝撃が加わり、スポーリングが生じるため、一般的に熱衝撃に強い炭素系原料がこれら鋼の連続鋳造用ノズルに用いられる。特に、鋳造開始時、連続鋳造用ノズル本体には大きな熱衝撃が加わるため、連続鋳造用ノズルをバーナーなどで予熱することが行われている。しかし、予熱時や鋳造中に連続鋳造用ノズルが酸化するため、一般的に連続鋳造用ノズル表面には酸化防止材が塗布されている。しかしながら、連続鋳造用ノズルを鋳造前に予熱しても、鋳造開始までの間に連続鋳造用ノズルの本体温度が低下し、連続鋳造用ノズルが鋳造初期で割れることがある。このため、予熱後の保温を適切に行うために、一般的に連続鋳造用ノズル外周に断熱材を貼り付けている。 In continuous casting of steel, the molten steel in the ladle passes through a long nozzle and is poured into the tundish. The molten steel in the tundish passes through the inner hole of the immersion nozzle and is injected into the water-cooled mold. For this reason, thermal shock is applied to the long nozzle and the submerged nozzle body, and spalling occurs. Therefore, carbon-based raw materials that are generally resistant to thermal shock are used for these steel continuous casting nozzles. In particular, since a large thermal shock is applied to the continuous casting nozzle body at the start of casting, the continuous casting nozzle is preheated with a burner or the like. However, since the continuous casting nozzle is oxidized during preheating or during casting, an antioxidant is generally applied to the surface of the continuous casting nozzle. However, even if the continuous casting nozzle is preheated before casting, the temperature of the main body of the continuous casting nozzle is lowered before the start of casting, and the continuous casting nozzle may be cracked at the initial stage of casting. For this reason, in order to perform the heat retention after preheating appropriately, a heat insulating material is generally attached to the outer periphery of the nozzle for continuous casting.
例えば、特許文献１は、連続鋳造方法に係るものであり、少なくとも浸漬ノズルの吐出孔を断熱材で覆い、当該浸漬ノズルを高周波誘導加熱により予熱すると、鋳造初期での割れの発生を抑えることができると記載されている。また、特許文献１の［００１３］段落には、断熱材として、主としてＡｌ２Ｏ３−ＳｉＯ２系耐火性セラミックファイバー（以下、ＲＣＦ）を含んで構成された断熱材、ＳｉＯ２−ＭｇＯ質のセラミックファイバー、Ａｌ２Ｏ３−ＳｉＯ２質の断熱キャスタブル等が例示されている。
また、特許文献２には、溶融金属をモールド内に供給するノズル本体と、このノズル本体の外表面に設けられた酸化防止用コーティングと、この酸化防止用コーティングを介してノズル本体を覆うように設けられたセラミックファイバー製の保温材と、この保温材の外表面に設けられた酸化防止用コーティングを有することを特徴とする浸漬ノズルが記載されている。
For example, Patent Document 1 relates to a continuous casting method. When at least the discharge hole of the immersion nozzle is covered with a heat insulating material and the immersion nozzle is preheated by high-frequency induction heating, it is possible to suppress the occurrence of cracks in the initial casting. It is stated that it can be done. [0013] In paragraph [0013] of Patent Document 1, as a heat insulating material, a heat insulating material mainly including Al 2 O 3 —SiO 2 refractory ceramic fiber (hereinafter referred to as RCF), SiO 2 —MgO-based material. Examples thereof include ceramic fibers and Al 2 O 3 —SiO 2 heat insulating castables.
Further, in Patent Document 2, a nozzle body that supplies molten metal into a mold, an anti-oxidation coating provided on the outer surface of the nozzle body, and the nozzle body is covered via the anti-oxidation coating. An immersion nozzle is described that has a heat insulating material made of ceramic fiber and an anti-oxidation coating provided on the outer surface of the heat insulating material.
ここで、ＲＣＦを含む断熱材を連続鋳造用ノズルに巻く際には接着剤が使用されるが、この接着剤とＲＣＦの反応により、ＲＣＦの断熱効果が低下するという課題があった。接着剤として無機系接着剤を使用すると、連続鋳造用ノズル使用前の予熱時に無機系接着剤が溶融してＲＣＦと反応することで、ＲＣＦの硬化、収縮が進み、断熱性が低下する。この課題に対して、特許文献３には、浸漬ノズルの外周にシート状セラミックファイバーを接着する浸漬ノズル用接着剤であって、コロイダルシリカ４０〜８０重量％と、アルミナ、シリカ、ムライト及びジルコニアの少なくとも一種以上からなる粉末状バルクファイバー６０〜２０重量％とのペースト状の混合物から構成される浸漬ノズル用接着剤が開示されている。 Here, an adhesive is used when a heat insulating material containing RCF is wound around a continuous casting nozzle. However, there has been a problem that the heat insulating effect of RCF is reduced due to the reaction between the adhesive and RCF. When an inorganic adhesive is used as an adhesive, the inorganic adhesive melts and reacts with RCF during preheating before using the continuous casting nozzle, so that RCF cures and contracts and heat insulation decreases. In response to this problem, Patent Document 3 discloses an immersion nozzle adhesive for adhering a sheet-like ceramic fiber to the outer periphery of an immersion nozzle, comprising 40 to 80% by weight of colloidal silica, alumina, silica, mullite and zirconia. An adhesive for immersion nozzles is disclosed which is composed of a paste-like mixture of 60 to 20% by weight of powdered bulk fibers composed of at least one kind.
しかし、ＲＣＦを吸い込むと生体内で溶解せず、発癌を誘発する恐れがあることから、平成２７年１１月に厚生労働省によりＲＣＦの規制が開始された。発癌性防止のためのＲＣＦの代替品として生体溶解性ファイバー（Bio Soluble Fiber：以下、ＢＳＦ）が開発された。ＢＳＦにはアルカリ金属系、アルカリ土類金属系の２種類ある。アルカリ金属系ＢＳＦ（ＡＭＳ−ＢＳＦ）としては、Ａｌ２Ｏ３−ＳｉＯ２−Ｋ２Ｏ系が、アルカリ土類金属系ＢＳＦ（ＡＥＳ−ＢＳＦ）としては、ＳｉＯ２−ＣａＯ−ＭｇＯ系がそれぞれ例示される。また、厚み３〜２５ｍｍ、かさ密度５０〜１５０ｋｇ／ｍ３程度の綿状に保型されたＢＳＦブランケットや、厚み１〜１０ｍｍ、かさ密度１００〜２５０ｋｇ／ｍ３程度のシート状に成形されたＢＳＦペーパーがある。ＢＳＦは上述のようにアルカリ金属またはアルカリ土類金属元素を含むため、人体に取り込まれても、生体内で溶解する。そのため、発癌の恐れが低い。しかし、酸化防止材（酸化防止用コーティング）を塗布した連続鋳造用ノズルに、ＢＳＦを断熱材として適用した場合、ＢＳＦと酸化防止材とが反応し、ＢＳＦの著しい変質または消失が起こる。この課題に対し、以下のような対策が講じられた。 However, since inhalation of RCF does not dissolve in vivo and may induce carcinogenesis, the Ministry of Health, Labor and Welfare started regulation of RCF in November 2015. Biosoluble fiber (hereinafter referred to as BSF) has been developed as an alternative to RCF for preventing carcinogenicity. There are two types of BSF, alkali metal and alkaline earth metal. Examples of the alkali metal BSF (AMS-BSF) include Al 2 O 3 —SiO 2 —K 2 O, and examples of the alkaline earth metal BSF (AES-BSF) include SiO 2 —CaO—MgO. Is done. The thickness 3 to 25 mm, BSF blanket and which is Hogata bulk density 50~150kg / m 3 approximately flocculent, molded thickness 1 to 10 mm, the bulk density 100~250kg / m 3 approximately sheet-like BSF There is paper. Since BSF contains an alkali metal or alkaline earth metal element as described above, it dissolves in vivo even if it is taken into the human body. Therefore, the risk of carcinogenesis is low. However, when BSF is applied as a heat insulating material to a continuous casting nozzle to which an antioxidant (antioxidant coating) is applied, the BSF and the antioxidant react to cause significant alteration or disappearance of the BSF. The following measures were taken to address this issue.
更に、特許文献４には、生体溶解性断熱材の層と耐火物構造体との間に、前記の生体溶解性断熱材及び前記の耐火物構造体との反応抑制層を備えた、断熱構造体（請求項１）；前記の反応抑制層は、１０００℃酸化雰囲気中熱処理後の化学成分としてＺｒＯ２及びＳｉＯ２を合計で９４質量％以上含有し、残部が前記以外の耐火性成分からなる、前記断熱構造体（請求項３）；前記の生体溶解性断熱材は、１０００℃酸化雰囲気中熱処理後の化学成分としてＳｉＯ２、Ａｌ２Ｏ３及びＫ２Ｏを合計で９０質量％以上含有し、残部が前記以外の金属酸化物、硼化物から選択する１種以上の成分からなる、前記断熱構造体（請求項７）；前記の耐火物構造体の、前記反応抑制層と接する面の一部又は全部に、１０００℃以下で一部又は全部が溶融して空気の通過を遮断する酸化防止材の層が設置されている、前記断熱構造体（請求項１０）；鋼の連続鋳造用ノズルの、大気又は酸化性ガスに接触する面の一部又は全部に前記の酸化防止材の層が設置され、当該酸化防止材の層の外面に前記の反応抑制層が設置され、さらにその外面に前記の生体溶解性断熱材の層が設置され、前記の酸化防止材の層の厚さは０．３ｍｍ以上１．０ｍｍ以下、前記の反応抑制層の厚さは０．６ｍｍ以上１．５ｍｍ以下、前記の生体溶解性断熱材の層の厚さは３ｍｍ以上である、前記断熱構造体（請求項１３）」が開示されている。また、特許文献４の［００３６］段落には、高温用ＢＳＦとして、Ａｌ２Ｏ３約３５質量％、ＳｉＯ２約３２質量％、Ｋ２Ｏ約２５質量％、ＺｒＯ２約７質量％の化学組成を有するものが開示されている。また、［００３９］段落には、Ｋ２Ｏの含量が概ね２０〜３０質量％であることも記載されている。 Further, Patent Document 4 discloses a heat insulating structure including a reaction suppressing layer between the biosoluble heat insulating material and the refractory structure between the biosoluble heat insulating material layer and the refractory structure. Body (Claim 1); The reaction suppression layer contains 94% by mass or more of ZrO 2 and SiO 2 in total as chemical components after heat treatment in an oxidizing atmosphere at 1000 ° C., and the balance is composed of other refractory components. The heat insulating structure (Claim 3); the biosoluble heat insulating material contains 90 mass% or more in total of SiO 2 , Al 2 O 3 and K 2 O as chemical components after heat treatment in an oxidizing atmosphere at 1000 ° C. And the balance is composed of one or more components selected from metal oxides and borides other than the above, and the heat insulating structure (Claim 7); the surface of the refractory structure in contact with the reaction suppression layer Part or all, part or all, below 1000 ° C A layer of an antioxidant material that melts and blocks the passage of air (Claim 10); part of the surface of a steel continuous casting nozzle in contact with air or an oxidizing gas Or the layer of the antioxidant material is installed in the whole, the reaction suppression layer is installed on the outer surface of the antioxidant material layer, and the biosoluble heat insulating material layer is installed on the outer surface, The thickness of the antioxidant layer is from 0.3 mm to 1.0 mm, the thickness of the reaction suppression layer is from 0.6 mm to 1.5 mm, and the thickness of the biosoluble heat insulating material is The said heat insulation structure (Claim 13) "which is 3 mm or more is disclosed. [0036] In paragraph [0036] of Patent Document 4, as BSF for high temperature, a chemical composition of about 35 mass% Al 2 O 3 , about 32 mass% SiO 2 , about 25 mass% K 2 O, and about 7 mass% ZrO 2 is used. What has a composition is disclosed. The paragraph [0039] also describes that the content of K 2 O is approximately 20 to 30% by mass.
しかしながら、特許文献４に係る発明では、酸化防止材の層と、生体溶解性断熱材の層との間に反応抑制層を設ける必要があり、更に、生体溶解性断熱材の層としてアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材として用いると、酸化防止材との反応を抑制できないという問題点もあった。 However, in the invention according to Patent Document 4, it is necessary to provide a reaction suppression layer between the antioxidant material layer and the biosoluble heat insulating material layer. Further, alkaline earth is used as the biosoluble heat insulating material layer. When used as a heat insulating material composed of a biosoluble fiber containing metal, there is also a problem that the reaction with the antioxidant cannot be suppressed.
従って、本発明の目的は、酸化防止材を塗布した鋼の連続鋳造用ノズルへ、アルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材を貼り付けるに際して、反応抑制層を設けることなく、アルカリ土類金属を含む生体溶解性ファイバーと酸化防止材との反応を抑制できる、鋼の連続鋳造用ノズルへのアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材の貼り付け方法を提供することにある。 Therefore, an object of the present invention is to provide a reaction-inhibiting layer when a heat insulating material composed of a biosoluble fiber containing an alkaline earth metal is attached to a steel continuous casting nozzle coated with an antioxidant. A method for attaching a heat insulating material comprising a biosoluble fiber containing alkaline earth metal to a nozzle for continuous casting of steel capable of suppressing the reaction between the biosoluble fiber containing alkaline earth metal and the antioxidant Is to provide.
酸化防止材を塗布した鋼の連続鋳造用ノズルに有機接着剤を用いてアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材を貼り付けると、予熱の際に断熱材の著しい変質または消失が起こる。これは、有機接着剤が予熱により消失し、酸化防止材とアルカリ土類金属を含む生体溶解性ファイバーが反応するためと考えられる。そこで、有機接着剤に耐火性材料を添加して上記反応を抑制することを検討した。耐火性が良好な耐火性材料として、アルミナ、ムライト、シリカなどが挙げられる。まず、アルミナを有機接着剤に添加してみたが、断熱材の変質や消失を抑制することはできなかった。次に、ムライトを有機接着剤に添加してみたが、アルミナと同様に抑制できなかった。これは、ＳｉＯ２、ＣａＯ、Ａｌ２Ｏ３が低融点物を形成して有機接着剤を溶解するためと考えられる。一方、シリカを有機接着剤に添加すると、断熱材の変質、消失を抑制することができた。なお、鋼の連続鋳造用ノズルに塗布した酸化防止材の上にシリカと有機接着剤の混合材料を塗布して乾燥させた後に、有機接着剤を用いて断熱材を貼り付けると、同様に断熱材の変質、消失を抑制することができることも判明した。
本発明は、上記知見に基づき完成したものである。
When a heat insulating material composed of biosoluble fiber containing alkaline earth metal is attached to a nozzle for continuous casting of steel coated with an antioxidant using an organic adhesive, significant deterioration of the heat insulating material during preheating or Disappearance occurs. This is presumably because the organic adhesive disappears due to preheating, and the biosoluble fiber containing the antioxidant and the alkaline earth metal reacts. Therefore, it was studied to suppress the above reaction by adding a refractory material to the organic adhesive. Alumina, mullite, silica etc. are mentioned as a refractory material with good fire resistance. First, alumina was added to the organic adhesive, but it was not possible to suppress the alteration or disappearance of the heat insulating material. Next, mullite was added to the organic adhesive, but could not be suppressed as in the case of alumina. This is presumably because SiO 2 , CaO, Al 2 O 3 forms a low melting point material and dissolves the organic adhesive. On the other hand, when silica was added to the organic adhesive, the heat insulating material could be prevented from being altered or lost. In addition, after applying a mixed material of silica and organic adhesive on the antioxidant applied to the nozzle for continuous casting of steel and drying it, and then applying a heat insulating material using an organic adhesive, heat insulation is similarly applied. It was also found that deterioration and disappearance of the material can be suppressed.
The present invention has been completed based on the above findings.
即ち、本発明は、酸化防止材を塗布した鋼の連続鋳造用ノズルへのアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材の貼り付け方法において、有機バインダーとシリカ原料よりなる接着剤を用いて、アルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材を貼り付けることを特徴とする酸化防止材を塗布した連続鋳造用ノズルへのアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材の貼り付け方法にある。 That is, the present invention relates to an adhesion method comprising an organic binder and a silica raw material in a method of attaching a heat insulating material comprising a biosoluble fiber containing an alkaline earth metal to a steel continuous casting nozzle coated with an antioxidant. Bio-solubility containing alkaline earth metal to continuous casting nozzle coated with antioxidant, characterized in that a heat-insulating material composed of bio-soluble fiber containing alkaline earth metal is pasted using an agent There is a method of attaching a heat insulating material made of fiber.
また、本発明の酸化防止材を塗布した鋼の連続鋳造用ノズルへのアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材の貼り付け方法は、前記接着剤が有機バインダーの含有量１０〜８０質量％、シリカ原料の含有量２０〜９０質量％であることを特徴とする。 Further, in the method for attaching a heat insulating material comprising a biosoluble fiber containing an alkaline earth metal to a continuous casting nozzle for steel coated with the antioxidant of the present invention, the adhesive contains an organic binder. It is characterized by being 10 to 80% by mass and a silica raw material content of 20 to 90% by mass.
さらに、本発明の酸化防止材を塗布した鋼の連続鋳造用ノズルへのアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材の貼り付け方法は、酸化防止材が鋼の連続鋳造用ノズルの外表面に塗布されていることを特徴とする。 Furthermore, the method of attaching a heat insulating material comprising a biosoluble fiber containing an alkaline earth metal to a continuous casting nozzle of steel coated with the antioxidant of the present invention is a method in which the antioxidant is used for continuous casting of steel. It is applied to the outer surface of the nozzle.
本発明の酸化防止材を塗布した鋼の連続鋳造用ノズルへのアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材の貼り付け方法によれば、有機接着剤にシリカ原料を添加するという簡便な手法により、予熱時の酸化防止材とアルカリ土類金属を含む生体溶解性ファイバーとの反応を抑制することができ、予熱時の断熱材の変質や消失を改善することができる。 According to the method for attaching a heat insulating material composed of a biosoluble fiber containing an alkaline earth metal to a steel continuous casting nozzle coated with the antioxidant of the present invention, a silica raw material is added to an organic adhesive. By this simple method, the reaction between the antioxidant during preheating and the biosoluble fiber containing an alkaline earth metal can be suppressed, and alteration and disappearance of the heat insulating material during preheating can be improved.
本発明は、酸化防止材を塗布した鋼の連続鋳造用ノズルへアルカリ土類金属を含む生体溶解性ファイバーから構成される断熱材を貼り付ける際に、有機バインダーとシリカ原料から構成される接着剤を使用するところに特徴を有するものである。 The present invention provides an adhesive composed of an organic binder and a silica raw material when a heat insulating material composed of a biosoluble fiber containing an alkaline earth metal is attached to a steel continuous casting nozzle coated with an antioxidant. It has the feature in using.
ここで、本明細書に記載する「アルカリ土類金属を含む生体溶解性ファイバー（以下、ＡＥＳ−ＢＳＦと記載することもある）」は、ＳｉＯ２含有量が７０〜９０質量％、好ましくは７５〜８５質量％、ＣａＯ＋ＭｇＯ含有量が１０〜３０質量％、好ましくは１５〜２５質量％、その他の成分５質量％以下（ゼロを含む）、好ましくは２質量％以下（ゼロを含む）の範囲内のものである。なお、その他の成分としては、例えば、Ａｌ２Ｏ３、Ｎａ２Ｏ、Ｋ２Ｏなどが挙げられる。本発明に使用する断熱材は、ＡＥＳ−ＢＳＦから構成されるもので、厚さ１〜２５ｍｍ、好ましくは１〜１０ｍｍのもので、綿状に保型されたブランケットやシート状に成形されたペーパーなどがある。 Here, the “biosoluble fiber containing an alkaline earth metal (hereinafter sometimes referred to as AES-BSF)” described in the present specification has a SiO 2 content of 70 to 90% by mass, preferably 75. Within the range of ˜85 mass%, CaO + MgO content of 10-30 mass%, preferably 15-25 mass%, other components 5 mass% or less (including zero), preferably 2 mass% or less (including zero) belongs to. As the other components, for example, Al 2 O 3, Na 2 O, etc. K 2 O and the like. The heat insulating material used in the present invention is composed of AES-BSF, and has a thickness of 1 to 25 mm, preferably 1 to 10 mm, and is formed into a blanket or a sheet formed in a cotton shape. and so on.
本発明に使用する接着剤を構成するシリカ原料は、シリカ純度が９０質量％以上のものであり、好ましくはシリカ純度が９７質量％以上のものである。シリカ原料の純度が９０質量％未満であると、鋼の連続鋳造用ノズルへ塗布されている酸化防止材と、ＡＥＳ−ＢＳＦとの反応を十分に抑制できないために好ましくない。 The silica raw material constituting the adhesive used in the present invention has a silica purity of 90% by mass or more, and preferably has a silica purity of 97% by mass or more. If the purity of the silica raw material is less than 90% by mass, the reaction between the antioxidant applied to the steel continuous casting nozzle and AES-BSF cannot be sufficiently suppressed, such being undesirable.
また、シリカ原料の粒度は、２００μｍ以下であることが望ましい。シリカ原料の粒度が２００μｍを超えると、鋼の連続鋳造用ノズルにＡＥＳ−ＢＳＦから構成される断熱材を貼り付け難くなることがあるために好ましくない。なお、シリカ原料としては、例えば溶融シリカ、珪砂、珪石粉などが挙げることができる。 The particle size of the silica raw material is desirably 200 μm or less. If the particle size of the silica raw material exceeds 200 μm, it may be difficult to attach a heat insulating material composed of AES-BSF to a steel continuous casting nozzle. Examples of the silica raw material include fused silica, silica sand, and quartzite powder.
シリカ原料の含有量は特には規定されないが、２０〜９０質量％の範囲内であることが好ましく、４０〜７０質量％の範囲内であることがより好ましい。シリカ原料の含有量が２０質量％未満であると、酸化防止材とＡＥＳ−ＢＳＦとの反応を抑制しにくくなるために好ましくない。また、シリカ原料の含有量が９０質量％を超えると、ＡＥＳ−ＢＳＦから構成される断熱材を鋼の連続鋳造用ノズルに貼り付けることが困難になるために好ましくない。 The content of the silica raw material is not particularly specified, but is preferably in the range of 20 to 90% by mass, and more preferably in the range of 40 to 70% by mass. If the content of the silica raw material is less than 20% by mass, it is difficult to suppress the reaction between the antioxidant and AES-BSF, which is not preferable. Further, if the content of the silica raw material exceeds 90% by mass, it is not preferable because it becomes difficult to attach the heat insulating material composed of AES-BSF to the steel continuous casting nozzle.
なお、シリカ原料は単一の粒度のものを使用することもできるが、粒度２００〜４５μｍの粗粒と、粒度４５μｍ未満の微粉の２種類を併用することがより好ましい。粒度の異なる２種類のシリカ原料を用いることで、シリカ原料の緻密性が向上し、より効果的にＡＥＳ−ＢＳＦと酸化防止材との反応を抑制することができる。ここで、接着剤中のシリカ原料粗粒の含有量は５〜２０質量％、好ましくは１０〜１５質量％の範囲内であり、微粉の含有量は３５〜５０質量％、好ましくは４０〜４５質量％の範囲内である。なお、本明細書に記載する「粒度」は、ＪＩＳ Ｚ ８８０１−１に準拠するものである。 In addition, although a silica raw material can also be used for a single particle size, it is more preferable to use two types of coarse particles having a particle size of 200 to 45 μm and fine powder having a particle size of less than 45 μm. By using two types of silica raw materials having different particle sizes, the density of the silica raw material is improved, and the reaction between AES-BSF and the antioxidant can be more effectively suppressed. Here, the content of coarse silica raw material in the adhesive is 5 to 20% by mass, preferably 10 to 15% by mass, and the content of fine powder is 35 to 50% by mass, preferably 40 to 45%. It is in the range of mass%. The “particle size” described in the present specification is based on JIS Z8801-1.
次に、本発明に使用する接着剤を構成する有機バインダーとしては、例えば、酢酸ビニル、フェノール樹脂、エポキシ樹脂などが挙げられる。有機バインダーの含有量は１０〜８０質量％、好ましくは３０〜６０質量％の範囲内である。なお、本発明において、無機バインダーは、バインダーを構成する無機成分がＡＥＳ−ＢＳＦと反応するために使用することができない。 Next, as an organic binder which comprises the adhesive agent used for this invention, vinyl acetate, a phenol resin, an epoxy resin etc. are mentioned, for example. The content of the organic binder is 10 to 80% by mass, preferably 30 to 60% by mass. In the present invention, the inorganic binder cannot be used because the inorganic component constituting the binder reacts with AES-BSF.
次に、本発明方法が適用される鋼の連続鋳造用ノズルの材質は、特に限定されるものではなく、公知・慣用の材質を用いることができ、例えば、アルミナ・シリカ・カーボン材質、ジルコニア・カーボン材質などの鋼の連続鋳造用ノズルを用いることができる。 Next, the material of the nozzle for continuous casting of steel to which the method of the present invention is applied is not particularly limited, and a known / conventional material can be used, for example, alumina / silica / carbon material, zirconia / A nozzle for continuous casting of steel such as carbon material can be used.
また、鋼の連続鋳造用ノズルへ塗布される酸化防止材は、特に限定されるものではなく、公知慣用の酸化防止材であればいずれのものでも使用することができ、例えば、ＳｉＯ２、ＳｉＣ、金属Ｓｉ、Ｂ２Ｏ３などを含み、融点４００〜１０００℃、好ましくは５００℃程度のものなどが適用可能である。なお、酸化防止材は、鋼の連続鋳造用ノズルの任意の部位へ塗布することができるが、少なくとも鋼の連続鋳造用ノズルの外表面に塗布されていることが好ましい。 Moreover, the antioxidant applied to the nozzle for continuous casting of steel is not particularly limited, and any known antioxidant can be used. For example, SiO 2 , SiC , Metal Si, B 2 O 3 and the like, and those having a melting point of 400 to 1000 ° C., preferably about 500 ° C. are applicable. The antioxidant can be applied to any part of the steel continuous casting nozzle, but it is preferably applied to at least the outer surface of the steel continuous casting nozzle.
上述のような構成を有する酸化防止材を塗布した鋼の連続鋳造用ノズルに、上記接着剤を用いてＡＥＳ−ＢＳＦから構成される断熱材を貼り付ける方法は特に限定されるものではないが、例えば、ＡＥＳ−ＢＳＦから構成される断熱材に上記接着剤を塗布した後、酸化防止材を塗布した鋼の連続鋳造用ノズルに貼り付けることができる。また、酸化防止材を塗布した鋼の連続鋳造用ノズルに上記接着剤を塗布した後、ＡＥＳ−ＢＳＦから構成される断熱材を貼り付けることもできる。その中でも、ＡＥＳ−ＢＳＦから構成される断熱材に上記接着剤を塗布した後、酸化防止材を塗布した鋼の連続鋳造用ノズルに貼り付ける方法を採用することで、複数枚の断熱材の端部を重ね合わせて隙間なく貼り付けることができる点で好ましい。なお、接着剤の塗布方法は特に限定されるものではなく、刷毛を用いて塗布する、スプレーで吹付けて塗布するなどの方法を採用することができる。また、接着剤の塗布厚みもまた特に限定されるものではないが、例えば３ｍｍ以下、好ましくは１ｍｍ以下とすることができる。 The method of attaching the heat insulating material composed of AES-BSF to the nozzle for continuous casting of steel coated with the antioxidant having the above-described configuration using the adhesive is not particularly limited. For example, after applying the adhesive to a heat insulating material made of AES-BSF, it can be attached to a steel continuous casting nozzle coated with an antioxidant. Moreover, after apply | coating the said adhesive agent to the nozzle for continuous casting of steel which apply | coated the antioxidant, the heat insulating material comprised from AES-BSF can also be affixed. Among them, after applying the above-mentioned adhesive to a heat insulating material composed of AES-BSF, by adopting a method of sticking to a steel continuous casting nozzle coated with an antioxidant, the end of a plurality of heat insulating materials It is preferable in that the portions can be overlapped and pasted without gaps. In addition, the application method of an adhesive agent is not specifically limited, The method of apply | coating using a brush, spraying with a spray, etc. is employable. Moreover, the application thickness of the adhesive is not particularly limited, but may be, for example, 3 mm or less, preferably 1 mm or less.
以下に、本発明例及び比較例を挙げて本発明方法を更に記載する。
まず、以下の表１に記載する配合割合にて、本発明例に使用する接着剤を、表２に示す配合割合にて、比較例に使用する接着剤をそれぞれ調製した。
Hereinafter, the method of the present invention will be further described with reference to examples of the present invention and comparative examples.
First, the adhesive agent used for a comparative example was prepared for the adhesive agent used for the example of this invention in the mixing | blending ratio described in the following Table 1, and the mixing | blending ratio shown in Table 2, respectively.
まず、鋼の連続鋳造用ノズルの外側の表面に、上記酸化防止材を厚さ１ｍｍに塗布した後、１０５℃で乾燥した。次に、所定の寸法に調整したＡＥＳ−ＢＳＦから構成される断熱材の表面に、表１及び２に記載する接着剤を所定の厚さに塗布した後、鋼の連続鋳造用ノズルの酸化防止材塗布面に貼り付けた。 First, the antioxidant was applied to a thickness of 1 mm on the outer surface of a steel continuous casting nozzle, and then dried at 105 ° C. Next, after applying the adhesive described in Tables 1 and 2 to a predetermined thickness on the surface of the heat insulating material composed of AES-BSF adjusted to a predetermined size, oxidation prevention of the steel continuous casting nozzle is performed. It stuck on the material application surface.
なお、鋼の連続鋳造用ノズルは、黒鉛２３質量％、シリカ１５質量％、アルミナ６２質量％からなるアルミナ−グラファイト材（ＡＧ材）より構成されるものであった。
また、鋼の連続鋳造用ノズルに塗布される酸化防止材は、ＳｉＯ２３０質量％、Ａｌ２Ｏ３１２質量％、Ｎａ２Ｏ８質量％、Ｋ２Ｏ３質量％、ＳｉＣ１１質量％、Ｂ２Ｏ３１５質量％、金属Ｓｉ２１質量％の配合を有し、外掛けで２質量％の有機バインダーを含有するものを使用した。
更に、ＡＥＳ−ＢＳＦから構成される断熱材のＡＥＳ−ＢＳＦの組成は、Ａｌ２Ｏ３２質量％、ＳｉＯ２７８質量％、ＣａＯ１質量％、ＭｇＯ１９質量％であり、断熱材は厚さ２ｍｍのものを使用した。
The nozzle for continuous casting of steel was composed of an alumina-graphite material (AG material) composed of 23% by mass of graphite, 15% by mass of silica, and 62% by mass of alumina.
Moreover, the antioxidant applied to the nozzle for continuous casting of steel is SiO 2 30% by mass, Al 2 O 3 12% by mass, Na 2 O 8% by mass, K 2 O 3% by mass, SiC 11% by mass, B 2 O. 3 A material containing 15% by mass and 21% by mass of metallic Si and containing 2% by mass of an organic binder as an outer shell was used.
Furthermore, the composition of AES-BSF of the heat insulating material composed of AES-BSF is Al 2 O 3 2% by mass, SiO 2 78% by mass, CaO 1% by mass, MgO 19% by mass, and the heat insulating material has a thickness of 2 mm. I used something.
断熱材を貼り付けた鋼の連続鋳造用ノズルについて、接着性及び反応性を下記の通り評価した。
接着性：
鋼の連続鋳造用ノズルの酸化防止材表面に断熱材を貼り付けてから１時間後に、接着剤の固化状況を確認することによって、断熱材の接着性を評価した。接着剤が十分に固化しておらず、断熱材を手で剥せるものを「△」、接着剤が概ね固化しており、断熱材を手で剥しづらいものを「○」、接着剤が完全に固化しており、断熱材を手で剥せないものを「◎」とした。得られた結果を表に併記する。
反応性：
断熱材を貼り付けた鋼の連続鋳造用ノズルを電気炉内に入れ、１３００℃で１時間加熱した後、常温まで冷却し、目視観察することにより反応性を評価した。断熱材が溶融したものを「１」、断熱材が殆ど消失しているものを「２」、断熱材が全体的に斑点状に消失しているものを「３」、断熱材が斑点状に消失しているものの、状態が比較的軽微であるものを「４」、断熱材の消失が殆ど認められず、僅かに薄肉化しているものを「５」、断熱材の消失、薄肉化が殆ど認められないものを「６」とした。得られた結果を表に併記する。
About the nozzle for continuous casting of steel which affixed the heat insulating material, adhesiveness and reactivity were evaluated as follows.
Adhesiveness:
One hour after applying the heat insulating material to the surface of the antioxidant of the nozzle for continuous casting of steel, the adhesiveness of the heat insulating material was evaluated by confirming the solidification state of the adhesive. “△” indicates that the adhesive is not sufficiently solidified and the insulation can be peeled off by hand, “○” indicates that the adhesive is generally solidified and the insulation is difficult to remove by hand, and the adhesive is completely “◎” indicates that the heat-insulating material cannot be peeled by hand. The results obtained are also shown in the table.
Reactivity:
A steel continuous casting nozzle with a heat insulating material was placed in an electric furnace, heated at 1300 ° C. for 1 hour, cooled to room temperature, and visually evaluated for reactivity. "1" indicates that the heat insulating material has melted, "2" indicates that the heat insulating material has almost disappeared, "3" indicates that the heat insulating material has generally disappeared in spots, and the heat insulating material has become speckled. Although it has disappeared, it is “4” when the state is relatively minor, “5” when the disappearance of the heat insulating material is hardly recognized and slightly thinned, and the disappearance of the heat insulating material is almost complete. What was not recognized was set to "6". The results obtained are also shown in the table.
本発明例１〜７は、シリカの総配合量を変化させた場合、本発明例８〜１０は、シリカの純度を変化させた場合、本発明例１１〜１６は、シリカ粒度を変化させた場合、本発明例１７〜１９は、有機バインダーの種類を変化させた場合、本発明例２０〜２２は、接着剤の厚みを変化させた場合を示しているが、いずれの断熱材も接着性、反応性は共に良好であった。 Inventive Examples 1-7, when the total amount of silica was changed, Inventive Examples 8-10 were changed in silica purity, Inventive Examples 11-16 were changed in silica particle size. In this case, Examples 17 to 19 of the present invention show cases where the type of the organic binder is changed, and Examples 20 to 22 of the present invention show cases where the thickness of the adhesive is changed. The reactivity was good.
これに対し、比較例１、２及び３は、接着剤の耐火性原料としてアルミナ、ムライト、ジルコンを配合した場合であるが、断熱材と酸化防止材との反応を抑制できないことが判る。
比較例４〜６は、接着剤のバインダーとして、無機バインダーを適用した場合であるが、断熱材と酸化防止材との反応を抑制できないことが判る。
上述のように、ＡＥＳ−ＢＳＦから構成される断熱材の接着性、反応性について、本発明例の優位性は明白である。
On the other hand, Comparative Examples 1, 2, and 3 are cases where alumina, mullite, and zircon are blended as the refractory raw material of the adhesive, but it is understood that the reaction between the heat insulating material and the antioxidant cannot be suppressed.
Comparative Examples 4 to 6 are cases where an inorganic binder is applied as the binder of the adhesive, but it is understood that the reaction between the heat insulating material and the antioxidant cannot be suppressed.
As described above, the superiority of the example of the present invention is obvious with respect to the adhesiveness and reactivity of the heat insulating material composed of AES-BSF.
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| JP2004244259A (en) * | 2003-02-13 | 2004-09-02 | Toshiba Ceramics Co Ltd | Adhesive for immersion nozzle |
| JP2013071848A (en) * | 2011-09-26 | 2013-04-22 | Ibiden Co Ltd | Heat insulator |
| JP2014141367A (en) * | 2013-01-23 | 2014-08-07 | Nichias Corp | Bio-soluble inorganic fiber and composition thereof |
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